Ester derivatives of chloromethyl dihydrosafrol



P Y E L ti ,Herman Wachs, Brooklyn, N: Y., a'ssignor to 'U.S.

v Industrial qheznical Inc., New York, N.'Y., a: 1

. .s rrqreii ni-efine e Ndmawingfi Application Apriizi; 1949,'Serial l -':::'-Ne.-:s 042;:In'Brazilltiarch2Q19117 ame, (01. zenassa .eThiS" invention. relates tornewiproductsiwhich. used as reactants fthe" reaction are useful ingredients of insecticides. i; tratedby the'following equation .L'Ihe products-pf: the,inventiomare;v esters of I hydroxymethyl dihydrosafrol and various-money OH2 GHa"-'-'9Ha" carboxylic acids,v namelypr unsubstituted, satue H26 H rated, straight-chain aliphaticacidsihaving from; one. to eighteencarbon. atoms; -unsubstituted, straight-chain aliphaticacids having from three to eighteen carbon atoms and one carbon to carbon double bond; monochlorinated, saturated, 10 straight-chain aliphatic acids'ha ving from two to eighteen carbon atoms; levulinic acid; phenoxyacetic acid and benzoic acid.

Hydroxymethyl dihydrosafrol is a material om-o-o-om In case the product is an ester of an acid havhavmg the formula ing a boiling point higher than that of water, 0 CHPCHPGH' such product, whether an ester of a chlorinated H acid or not, may be prepared simply by heating 2 \O equimolecular quantities of hydroxymethyl d1- hydrosafrol and the acid in the absence of an CHZOH esterification catalyst, the reaction being carand may be prepared from chlormethyl dihyried to completion by distilling the water of esterdrosafrol in accordance with the teachings of my ification from the reaction mixture with the aid copending application, Serial No. 658,872, filed of benzene in the known manner.

April 1, 1946, of which application the present The following table contains data obtained in application is a continuation-in-part. the Pest-Grady test on housefiies using various The new products, when they do not contain products falling within the scope of the present chlorine, are suitably prepared by heating the invention:

I 11 III IV Add Boiling range, C, at mm. Hg 2 1%+30 as pressure gggg gg Kill/ r: 9ff %l ll/O%J% Formic l20-3/1. 0.13 0.45 0.91 0.55 A ma 153-1 1 0. 4s 0. s9 0. 97 0. 79 n-Butyric 182/9. o. 29 1. oo o. 96 0. s5 n-Dodecyl 160-186/0 5 o. 02 0.14 o. 98 0.87 lO-Undecyl 1744 0 s 0. 2e 0. 79 o. 94 0. 5a O1eic 205-18/0 R 0. 89 0.70 Levulinic 130-(189)-195/1.5 0.01 0.24 0.81 0. 98 Phenoxyacetic 173(185)-224/0.5 0.00 0.19 0.89 1.06 IO-Chloro-undecyl- 165-190/0 5 0. 15 0. 4s 0. s9 0. s5 Benzoic Melting point,53-54C 0.08 1.48 0.91 0.66

anhydrous sodium salt of the acid in contact In the preceding table, 0. T. I. signifies the with an equimolar quantity of chloromethyl di- Oflicial Test Insecticide, a solution of 100 mg. hydrosafrol, the reaction mixture also containof pyrethrins in odorless kerosene. ing a small percentage of the free acid. The re- The column headed I gives the ratio of the action mixture is then stirred at 140-160 C. for knockdown of a solution of 2% of the product eight hours. After cooling, the reaction mixin odorless kerosene at the end of 10 minutes ture is taken up in benzene, and is thereafter to the knockdown of the O. T. I. at the end of Washed with water and sodium carbonate solu- 10 minutes. tion to remove the excess acid. The product is The column headed II gives the ratio of the recovered by distillation of the reaction mixture kill at the end of 24 hours of a 2% solution of inthe usual manner. For example, when chlorothe product in odorless kerosene to the kill of methyl dihydrosafrol and sodium acetate are the O. T. I. at the end of 24 hours.

The column headed III gives the ratio of the knockdown at the end of minutes of a solution of 1000 mg. of the product and 30 mg. of

pyrethrins in 100 ml. of odorless kerosene to the knockdown of the O. T. I. at the end of 10 minutes. s X

The coliihm headed IV gives the ratio of the kill at the end of 124 hours of a solution of "1000 mg. of the product and 30 mg. of pyrethrins in 100 ml. of odorless kerosene to the kill of the" O. T. I. at the end of 24 hours.

Using the procedures described above, various other products falling within the scope of this invention may be prepared 'usihg, the ma ner described above, palmitic acid, caproleic,

lauroleic acid, palmitoleic acid, acrylic acid,

monochloroacetic acid, alpha-chloropropiohic acid, beta-chlorobutyric acid, acids formed By the addition of hydrogen chloride to any of the preceding unsaturated acids, etc.

The products of this invention may be employed in the conventional ianherin insecticidal in \rhich A is the acyl radical of a monocar- .bo xylic acid selected from the group consisting of unsubstituted, saturated, straight-chain aliphatic acids having from one to eighteen carbon atoms; unsubstituted, straight-chain aliphatic acids havingfrom three to eighteen carbon atoms can one carbon to carbon double bond; mbnoemarmiaed, saturated, straight-chain aliphatic acids having from two to eighteen carbon atoms; levulinic acid; phenoxyacetic acid and benzoic acid.

2. The compounds of claim 1 in which A is the acyl radical of an unsubstituted, saturated, straight cham aliphatic acid having from one to eighteen carbon atoms. 5 a I x 3. The compounds of claim 1 in which A is the acetyl radical. a

4.- The compounds of clai'ml in which -A is the acyl radical of levulinic acid. r A

5. The eompoundsnf claim 1 in which A acyl radical of Iphe'nox yacetic acid.

- WACHS.

is the No references cited. 

1. THE COMPOUNDS OF THE GENERIC FORMULA 